Iron(II) Phthalocyanine Adsorbed on Defective Graphenes: A Density Functional Study

Abstract

The adsorptions of iron(II) phthalocyanine (FePc) on graphene and defective graphene were investigated systematically using density functional theory. Three types of graphene defects covering stone-wales (SW), single vacancy (SV), and double vacancy (DV) were taken into account, in which DV defects included DV(5-8-5), DV(555-777), and DV(5555-6-7777). The calculations of formation energies of defects showed that the SW defect has the lowest formation energy, and it was easier for DV defects to form compared with the SV defect. It is more difficult to rotate or move FePc on the surface of defective graphenes than on the surface of graphene due to bigger energy differences at different sites. Although the charge analysis indicated the charge transfers from graphene or defective graphene to FePc for all studied systems, the electron distributions of FePc on various defective graphenes were different. Especially for FePc@SV, the d xy orbital of Fe in the conduction band moved toward the Fermi level about 1 eV, and the d xz of Fe in the valence band for FePc@SV also moved toward the Fermi level compared with FePc@graphene and other FePc@defective graphenes. Between the planes of FePc and defective graphene, the electron accumulation occurs majorly in the position of the FePc molecular plane for FePc@SW, FePc@DV(5-8-5), and FePc@DV(5555-6-7777) as well as FePc@graphene. However, electrons were accumulated on the upper and lower surfaces of the FePc molecular plane for FePc@SV and FePc@DV(555-777). Thus, the electron distribution of FePc can be modulated by introducing the interfaces of different defective graphenes.

Phthalocyanine Adsorbed on Monolayer CrI3: Tailoring Their Magnetic Properties

“…In order to explore and utilize the similarity of Fe-Pc to the active site of hemoglobin, we consider a controllable supporting layer that interacts with Fe-Pc. Typically, in such cases, single-layered (2D) materials are good candidates. − One of these, chromium iodide (CrI 3 ) is a single-layer magnet, is structurally stable, and can provide a supporting layer for planar ligand surfaces. In addition, CrI 3 is ferromagnetic and can couple with the magnetization of the Fe-Pc molecule, while having tunable electronic and magnetic properties under the influence of external stimuli, such as strain and electric field. , A selective modification of magnetic anisotropy in Fe-Pc molecules has been previously demonstrated by Lisi et al, highlighting the role of structural symmetry disruption .…”